Petroleum wax-ethylene vinyl acetate copolymer composition



June 15, 1965 A. OKEN 3,189,573

PETROLEUM WAX-ETHYLENE'VINYL ACETATE COPOLYMER COMPOSITION Filed Oct. 1. 1962 4 Sheets-Sheet 1 ETHYLEIIE'I vum ACETATE COPOLYIER nx BLENDS IEIGIIT '1. mum/mm mm: corounsn m mun IEIGHT '1. m m mm ISO 40 50 EIGHT. VIIYL ACETATE Ill ETHYLEI EI VINYL ACETATE COPOLYIER INVENTOR AARON OKEN BY FM 9. A 6EIT June 15, 1965 A. OKEN 3,189,573

PETROLEUI VIAX-ETHYLENE VINYL ACETATE COEOLYMER COMPOSITION H.106 Oct. 1. 1962 4 Sheets-Sheet 3 comm: incur, uusooo n mvsmox AARON OKEN BY 130M 8, 6......4

AGENT June 15, 1965. A.'OKEN PETROLEUM WAX-ETHYLENE VINYL ACETATE COPOLYMER COMPOSITION 4 Sheets-Sheet. 4

'- il -11w Oct. 1'. 1962 o a T A. A 52352522.;5.2;: s as. E.

EIGHT 'Io ETHYLElE/VIIYI. ACETATE CQPOLYIER l o o W N M I 3 ll BLEND INVENTOR AARON OKEN AGENT 7 PETROLEUM WAX-ETHYLENE VINYL ACETATE COPOLYMER COMPOSITION Aaron Oken, Kennett Township, Pm, assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a

corporation of Delaware 7 Filed Oct. 1, 1962, Ser. No. 227,356 21 Claims. (Cl. 260-285) This is a continuation-in-part of my copending application Serial No. 24,945 filed April 27, 1960, now abandoned which in turn is a continuation-in-part of my earlier application Serial No. 788,708, filed January 26, 1959,

i now abandoned.

This invention relates to new compositions of matter and, more particularly, this invention relates to novel coating compositions containing specific amounts of certain ethylene/vinyl acetate (E/VA) copolymers and petroleurn wax in combinations that have superior and unexwide variety of applications.

. Insofar as wax coating compositions are described in the literature, most of the art analogous to the present invention relates to compositions which contain a number of constituents. I These compositions containing many components reflect efforts that have been made to impart to the wax such properties as adhesiveness, heat-sealability, flexibility, hardness, gloss, high blocking temperature, and other desirable characteristics.

In US. Patent 2,877,196 to Frederick P. Reding, compositions consisting predominantly of petroleum wax with 0.1 to 20% by weight of E/VA copolymers are disclosed. By theme of E/VA copolymers containing to 25%, preferably to by weight of copolymerized vinyl acetate, wax compositions having improved ductility and increased tensile strengths over unmodified wax or polyethylene-modified wax are obtained. The E/VA copolymet-wax blends are more compatible than polyethylenewax blends as indicated by the temperature differential between the cloudpoint or haze point of the blend and the melting point of the wax. The patent points out that compatiblity is an important property since two-phase mixtures show little improvement over unmodified wax. In addition, compatibility of the wex blend, in particular,

the haze point of the blend, is of considerable importance in impregnating and coating operations. In these operations, the temperature of the wax melt is maintained as low as possible to permit the coating to set quickly, to avoid oxidative degradation of the wax and to avoid damage to heat-sensitive substrates being coated. With a small temperature differential between the haze point of the wax blend and the melting point of the wax, it is possible to operate at the low temperature desired.

The Reding patent further discloses that wax compositions containing up to about 50% by weight of E/VA are not homogeneous and give some separation of copolymer. In order to prepare a truly non-separating wax compEsfltion, an E/VA content of 0.1 to 10% by weight is required.

' In contrast to the high-wax content compositions of the Reding patent and the incompatible blends obtained with higher concentrations of E/VA in the blend, I have found that remarkably flexible and compatible compositions are obtained if a critical relationship is maintained between the percentages of wax and E/ VA copolymer in the blend, the copolymerized vinyl acetate content of the E/VA copolymer, and the melt index of the E/VA copolymer.

United States Patent 0 20 A study'of the prior art will disclose numerous combi- FIGURE 1 is a graph in which contour lines are shown which outline E/VA-wax blend compositions having haze I pomts a given number of degrees (centigrade) higher than the melting point of the wax. Thus, the two contour lines, AT ,=5, indicate the relationship required between the E/VA copolymer and wax contents of the blend and the vinyl acetate content of the E/VA copoIymer, to yield compatible blends having haze points within 5 C. above the melting point of the wax. AT, is defined as the temperature differential in degrees centigrade between the haze point of the E/VA-wax blend and the melting point of the wax.

The closed area ABCD of FIGURE 1 represents my' compositions which have the percentage compositions of wax and E/VA copolymer in the blend and weight per centage of vinyl acetate in the copolymer, required to yield a compatible composition, that is one having a haze point within 5 C. of the melting point of the wax. De-

creased paper samples, respectively, at a constant coating weight. FIGURES 3 and 5 show the etfect of coating weight on the water vapor transmission rate of flat and creased paper samples, respectively, at a constant E/VA concentration in blends with five different petroleum waxes.

FIGURE 6 is a graph showing the effect of melt index on the minimum E/VA concentration in a wax blend required to provide sufficient flexibility that coatings on paper will retain their moistureproof properties after flex- My compositions containing the higher amounts of E/VA and within the closed area ABCD of FIGURE 1 and having the aforementioned critical melt index relationship, exhibit far greater heat-seal strengths and an entirely different order of flexibility than the prior known wax compositions containing 1 to 20% E/VA. The compositions also differ in other respects. Thus, while both compositions are heat-sealable and moistureproof, the prior compositions are predominantly wax compositions and have viscosities that approach those of the petroleum waxes at temperatures of about 60l00 C., i.e., in the melting range. Such E/VA wax compositions are easily applied at low temperatures by dip coating or hot-melt v coating. The thermoplastic compositions of the present invention must be heated to at least -175" C. in order to be sufficiently fluid for conventional hot-melt coating equipment and technique. However, because of their compatibility, they can be applied conveniently by conventional extrusion techniques at temperatures only slightly above the melting point of the wax. These compositions are especially adaptable for paper, paperboard, synthetic polymer films, aluminum foil and other substrates that are subject to flexing and wear, since they are extremely flexible and tough. Coatings of such composi-v tions remain heat-sealable and moistureproof even after repeated creasing and flexing.

It is an object of the present invention to provide a new coating composition that is heat-sealable and moistureproof.

It is another object of the present invention to provide a new coating composition that is extremely flexible and tough.

Patented June 15 I965 th pres nt inv nt o t pm .p'u n e appli to enhextw ee e be -m et "5:; is bblpvie e ttete having a. nexle ans 1!. eeelahle e fine e QB- ill ur e eb'iee i a nr' iid flexib nd. m eti le e mpe en and o h .Qbieets are ae em i hed w h. em: t ne le e 'n' ie ly f tre vm Wa en e tl y ne and viny eee ate he w i ht perlynier the emveei en an a i e n t enel mf 41.1 the eldsed area A C i when? sit the 'pemae ew in he r e w n 'E .Q FIGURE 1 i dep wiem the me eenalm efeee. i e fin je b v he eqeetie "w M! eepeeeeet the m lt ind x, e t e el in n v$ i9 Yield im n i ibn o s fiha p ne! eea d h r with ret n it t'fiexin The eheve. eque- L, 35%. w ee is in iiee ed, 1 f,-

at le els 9f' f eqn yml r in t com- 1 e e m lt in ex Qt thee neliimer i Y ae q qlymer in th mnae-m ze 0i "YiPYl Iae ta e in men by a int W hin the lee r fll' sible I .teugh' i I, x gro n about 9.1 to about 500. gtnneett ene' entai n m r th n 60% b be intet eefi be us my eempe t ens' are we; more than 6 e iieflY Th E YA ol'ec tlY than wait; it is obviously de- Qi 'P ein n ae mi e web; as Y He Co shanty; obtaining"the desired flexibility m Pepe? eeteew m om 11mg lar m e Qt eenelvm r h e li ettenlefl preferred ompos t n 1 1 9 Wei petem f a am: 40 l ii E VA ee oliime e ai i 28' at 1 f eepoli m i ed Vinyl e a ef we mamas. r er t above i the tentativeA S TM test method D 1238- Moleculatf weight of the copoly ner is an inverse fun ion'ofthe mdt index; An alternate method to indije er'we ish he E YAe P IYmer is b 1ts inh fentyiscosi ty as determined with 0.25 to: the. copolytner in tqlnene at 30 C. E/VA rsiwith aninhere'nt vis coeity 'of 0.5-1.5 are suitin this invention and copolyrners having an o sity of 0.6-},2 ai e preferred, It has been a A?! eempeeiti ne eo a n E/VA po ym s haying inhelfent viscosities lower than about 0.5 do not 's nfl icient etrength to! most applications. Copoly- 1;! rs of higher inhetent i scqsities than 1.5 are difiic'ult p epat'eiihde: conditions which are practical commern g m-qxi nate telationship between me]! index and nh etent'YiecosityoI E/YA copolymers. is indicated iab e lik me t iae ee ef e Y eepelymeee e Qt gthi t e te me int sh pe 0 that'the min mum /V I material ha i g a 'elti' e nt 653 e t indem Inherent 0 T e m etreleutn w x" as used o Pa afl -and mi teetyst ll'j. f is a mixture, of solid hyqt oca ns de head wax distillate fleet? distillationof petrol wax contains hydroca p 7 W czs lr z'sflwt i ee erle e a Mi ry e tn w is Qbt n'd' f om Still i u em, the fre tie el I il e It fie om em fin Wf x'i'h ha in car s he hql eula'rw i'sht It more plastic than parafljn wan a of about 130. 200 'FQ P aff n Wax is he nr ferred. we; Pee ett m i tueenreefineit an' LT. a d i n parafiifi wi XesI neeneral H h y r fin d m r erystal it e available bjlt are more cotly e ivalent lo prope i s he e l m te 9f th n an vin aeetate my comp si iq en 'he'n ena' ed I! met! teen in the art. Thus, the picice'duieisfdefstgtyibe 2,200,429. or 2,703,794 r emen of 'th op ly ei we be de' n y is or y s p nifie' ien num ,de. T e qwin exampl fut e illti ate. posifins Exem t;

-E VA. eo el m t eomneeitieee 'e new In heating a parafiin ax hai in inn; 1' I w t vary amounts f A co posi i n c' m ntn new 1 t 69% h! F A set e of RNA ob y ne s eenta i iz O ee e metiz d v n l 'a e atew e po nt t se inixtuit fs w r det ing the molten n ixture s at a iate o e, n observ n t emb l et'ute at 1th I! be n lqudy due te p i a e. eene The da e 9 j e n m w e Heed. tour lines of constant AT (tent; ta tween the haze point and melting t oithe in FIGURE 1. This fig re indicate; that'the aie t; p a u a dep den even b th he" tent of the E/VA and the E/VA con ent Below about 26% 'vinyl acetate in the points of blends inerease canoe then level off at a temperature which is a mac; vinyl acetate content. Abo ve abo tilt 3.0%. haze points increase bl iefly as E/YA tiqrt entt blend increases and then neclpeasc tapidl y with a increase in E/ VA concentration to tenihegtam re sl C. greater than the melting point of; the w it. pie, one copolymer containing 36.0% yiyl age a haze point of 97 C. (AT 4 2 at a 5% centration and a haze point of 5.'I (AT =2) at 50% E/VAconcentration.

melting points than the material used in Example 1.

Example 2 .Pigment (TiO )'-coated sulfite paper (25 lb./ ream) was coated on the pigmented side with a variety of E/VA-wax blends by various methods including hot-melt coating, 1 extrusion coating and solvent coating. The coated papers were tested for water vapor transmission (WV I of fiat and creased samples. The results obtained are summarized in Table II.

should be no more than about 50% greater than that of the flat sample and both should be below about 3.5.

g./ 100 in. /24 hours, when determined by the method described in this example. An alternate and preferred criterion of acceptable moistureproofing is that the abso lut increase in water vapor transmission of the creased sample over the fiat sample be no more than 0.75 g./ 100 in?/ 24 hours. Water vapor transmission rate tests provide not only a measure of the absolute moisture vapor permeability but also a measurement of the flexibility of coated paper samples, and thereby a measurement of the flexibility of the coating composition. E/VA-wax compositions are considered to be flexible if they provide moistureproof coatings on paper, that is, coatings which show a difierential of 0.75 g./ 100 in. /24 hours or less between the flat and creased water vapor transmission rates.

The results of Example 2 further show that compositions containing microcrystalline wax are not as effec- TABLE II EIVA WVT b (g. H Pnrnftin 100 in. /24 hours) wax, M.P. Method of Loading, Percent Inherent Percent F. application lb./rcum yl scosity I in wax Flat Greased acetate blend 27. 9 0. 97 40 147 Extrusion l9. 8 1. 0 1. 0

I Determined with 0.25% by weight of E/VA copolymer in toluene at 30 C.

5 Water vapor transmission reported for initial 24 hours at: 100 F. and vs. 5% relative humidity.

' Ratio of linear crease (in.) to area (in. )=l.63. 4 Microcrystalline wax.

The results show that there'is a correlation between the water vapor transmission of the coated paper after creasing and the percentage of E/VA in the E/VA-wax composition. Based on these results, it is necessary, to be certain of acceptable moistureproofing of creased paper samples, to use an E/VA-wax coating which contains more than 30% E/VA. Of the'two E/VA-wax compositions having an E/VA content of 30%, one gave acceptable moistureproofing of creased paper samples, while the other did not. The E/VA giving acceptable results had a melt index of 25 while that giving unacceptable results had a melt index of about 140. (Table I was used to correlate'melt indioes with the inherent viscosities shown in Table II) One criterion of acceptable moistureproofing is that the water vapor transmission of the creased sample tive for moistureproofing as parafiin wax compositions. However, the addition of E/VA copolymer did result in the creased sample having essentially the same moistureproofing properties as the flat sample.

Example 3 In order to define more exactly the minimum content of E/VA required in the blend for acceptable moistureproofing of creased paper samples, a statistically designed experiment was carried out using a single E/VA copolymer containing 28% vinyl acetate and having a melt index of 15. Five-different petroleum waxes were e Determined at F. and 90% RH. according to TAPPI T464m-45. 5 Prepared according to TAPPI T4ti5sm52.

P 7 For each of the five sets E/VA-wax blends, a central composite rotatable design as described by W. G. Cochran and G. M. Cox, Experimental Designs, 2nd edition, John Wiley & Sons, New York, 1957, pages 335- 375 was used as the experimental model in determining the Water vapor transmission rates (flat and creased) of the ElvA wax coated paper as functions of the E/VA concentration and the coating weight. In this design, the E/VA concentration was varied from 11 to 39% andthe coating weight from 6:5 to 23.5 lb./ 300 ft The design values for E/VA concentration and coating weight along with the coating weight actually obtained- Ioreach runare shown in Table IV.

were applied with the melt temperature between 180 and 210 F. Blends above 25% E/VA were applied at;

The data obtained from determination of thelwater vapor transmission rates (WVTR) of flat and creased TABLE IV Coded values I Actual Actual coating weights obtained Coating Run percent No. EIV A X; X; Wax A Wax B Wax C Wax D Wax E See the following table:

Coded values 4 2 1 0 +1 /2 m, Percent EIVA in blend"; u as 39 Kg, Coating weight, Ill-[3,000 RA--. 6. 5 9 15 21 23. 5

' The E/VA-wax blends and coated papersamples were coated paper samples at 100 F. and 90% RH. according to TAPPI T464m45 are shown in Table V. The creased samples were prepared according to TA'PPI T465sm-52.

TABLE V Water vapor transmission rate (gJlOO in. /24 hours) Coating Run No. Wax A Wax B Wax c Wax D Wax E Flat Greased Flat Greased Flat Greased Flat Greased Flat; Crossed 0. 12. 4 0. 33 7. 1. 41 5. 08 0. 28 6. 53 0. 51' 4.37 0. 30 9. 57 0.36 7. 83 1. 05 5. 29 0. 65 6. 80 1. 25 8. 0. 17 7. 30 0.15 3. 68 0. 34 1. 96 0.15 3. 92 0. 54 4. 40 0. 46 0.80 0. 43 1. 00 1. 05 2. 19 0.24 0. 69 2. 12 4.85 0. 25 0. 40 0. 32 0. 40 O. 77 0. 98 0. 17 0. 33 l. (I) 1.34 0. 58 0. 0.36 0. 56 1. 15 1. 16 0. 18 0. 49 1. 15 V 1.77 1. 92 12. 4 0.37 6.00 2. 69 11. 0. 46 6.21 1. 63 6.18 0. 25 0. 47 0. 21 0. 87 0. 56 0. 86 0. 22 0. 35 0. 82 1. 15 0. 19 0. 61 0. 20 0.49 0.91 1. 17 0. 17 0. 1. 04 1. 74 O. 24 0. 61 0. 20 0.99 0. 82 1.07 0.30 0.38 1. 10 1. 1B 0. 13 0. 40 0. 24 0. 79 t]. 98 1. 28 0. 32 0. 88 1. 22 1. 80 0. 22 1. 21 0.28 0.64 1. 32 1. 62 0. 22 1. 68 1.15 1. 65 0. 22 0. 78 0. 25 0. 62 0. 96 1. 27 0. 26 1. 12 1. 75 2. 47

p 220 250 F. using a laboratory air motor mixer. Blends containing more than 25% E/VA were prepared in a sigma. blade mixer at 220 F. These blends were then .solidi-fied for storage and remeltedin the coater feed The E/VA-wax blends were applied to the wire side of a 22 lb. bleached sulfite paper by a method in which the paper kisses a heated applicator roll which is running flooded in a pan containing the molten E/VA-wax blend. The applicator roll, driven at the same speed X '=E/VA- concentration and direction as tbe'paper web, transfers a controlled 75 X =coating weight B ,'B B B B B =calculated coetficients.

Using log Y as the function for the fiat and creased water vapor transmission rates, the coefiicients in Table VI were calculated.

exhibits acceptable moistureproofing as evidenced by the between the fiat and creased WV IR. The creased WVTR TABLE VI ranges from 0.5 g. 11 100 in. 24 hrs. for the high melt; FLAT WATER VAPOR TRANSMISSION RATES ing point parafiin blends to 1.8 g./100 mi /24 hrs. for the I microcrystalhne blends. By comparison, a 1b./3000 w A W3x B Wu C wax D wax E ft. extrusion coating of low density polyethylene has flat and creased values of 1.4 g. H O/ 100 lof /24 hrs. "Ihus, 1 2 M995 paper coated with E/VA-wax blends containing 25% or I -0. 1115 0. 1.21 322 g-figg 10 more resin is flexible and has water vapor barrier prop- 8152 I8j$ 1 1 Z 1 erties at least equivalent to paper extrusion coated with 07 0023 0. (D10 0. 0. 00:1 pglyethylene. V M023 M033 M055 2 The absolute increase in the WV IR caused by creasing I paper coated with blends containing more than 25% E/VA GREASED WATER VAPOR TRANSMISSION RATES 5 was about the same for all of the waxes tested. The dif- Y i ferences in the absolute creased values correspond to 1'"'" i 8160 -ifigi; iIiS -51 35 3333 the variations in the fiat values for the wax blends. Thus, 44713 M424 the flexibility of the wax does not have an etfecton the 1: 313% l i z 31% 81% 31% differential between the flat and creased WVTRat E/VA 4-0207 "M031 concentrations above At E/VA concentrations less H w I r than 25% the flexibility of the wax used does affect the v The equations obtained when using these coefliclents creased WVTR, v l 800d fit with t e data l1 1 T1118 means The coating weight necessary for aflexible coating is that better than 90% of the var at on in he data could shown by FIGURE 5 to be about 12 1b./3000 it, No be accounted for by the six terms of the equation. These 25 significant improvement was obtained with coating weights equations were thenused t0 d fi e the're1atl0nSh1P 0f greater than 15 1b./3000 it. Therefore, to obtain a Water vapor tralflsm on rate to the E/VA concentratio flexible, moisture vapor barrier on this particular grade in the E/VA-wax blends and the eoating'weights of the of paper, a blend of 25% E/VA in wax, applied at blends within the experimental region as shown 1n FIG- 1b./3000 ftP, is required.

URES 5 I Exam le 4 Q As shown in FIGURE 2 the addition of E/VA to the p four paraflin Waxes did not significantly affect the fiat The foregoing example demonstrated that a minimum WVTR of the unmodified waxes. These values are 0.2- of 25% of an E/VA having a vinyl acetate content of 0.3 g. 11,01100 inF/24 hrs. for the three higher melting 28% and melt index of 15 was required for an E/VA- 7 point paraflin waxes and 0.8 g. H,0/'100 inP/24 hrs. for wax blend to provide acceptable moistureproofing of the low melting point paraflin waxall at a constant creased paper samples. To define further the variables coating weight of 15 lb./3000 ftF. FIGURE 2 also affecting the minimal requirements of E/VA in the E/VA- shows that the flat WVTR for the microcrystalline-E/VA wax blend, paper samples were coated as in Example 3- coated paper increased with increasing E/VA concentrawith the compositions indicated in Table VII. Paraflin tions and leveled out at 25% E/VA with a value of 1.3 g. wax B in Example 3 was used in all the E/VA-wax blends. H,0/100in. /24 The data obtained for the WVIR of flat and creased FIGURE 3 shows the effect of the coating weight on samples by the method used in Example 3 are also sum 7 the flat WVTR at a constant E/VA concentration of 30% marized in Table VII.

TABLE VII E/VA copolymer Water vapor transmis Coating sion rate Coating weight Run No. 7

Percent Melt Percent in it. Flat Greased VAc index wax blend 2s 25 15 9 1.07 14.9, 23 25 15 21 0.29 4.34 2s 25 a5 9 0.21 0.01 28 25 a5 21 0.10 0.22' 20 25 25 15 -0.27 -1.a9 as 25 15 0 0.10 10.1

33 25 15 21 0. 30 3.90 as 25 a5 9 0. 24 0.98 33 25 35 21 0. 24 0.40 33 25 25 15 -0.33 -1.41 32 15 25 15 0.11 0.04 28 105 15 15 0.35 8.! as 105 25 15 50.24 -01 as 105 35 15 0.23 0.01 21 3 15 15 0.40 3.9 27 a 25 15 0.21 0.43 21 3 a5 15 0.35 0.40

- Average of 4 coating runs. b Average 01'2 coating runs Average of 3 coating runs.

This shows that little improvement was obtained in the Analysis of the data obtained in coating runs 1-10 flat WVTR at coating weights above 15 lb./3000 ftP. indicates that acceptable moistureproofing of coated paper The eflect of the E/VA concentration on the creased WVTR of the coated paper is illustrated in FIGURE 4 at a constant coating weight of 15 lb./3000 ftF. This shows that paper coated with blends containing 25% samples, as indicated by a difference in the flat and creased WVTR values of 0.75 g./ 100 in. /24 hrs., is obtained at an E/VA concentration of 28% with a coating weight of 15 lb./3000 ft. for the two E/VA samples having a melt or more E/VA has excellent resistance to creasing and index of 25 and vinyl acetate contents of 28% and 33%.

- This indicates that, within the vinyl acetate range between .lines AF and DE of FIGURE 1, an E/VA copolymer with 1 I 1 "a melt index of 25 must be present at a 28% level to provide await-composition with sufficient flexibility to give acceptable moistureproofing of creased paper samples. It mum indicates that'within this range of vinyl acetate,

the factor which determines the minimum amount of 7 E/VA. copolymer required is the melt index. This is further demonstrated by the results obtained in coating shows that a concentration of 35% of E/VA having a melt index of 165 and a vinyl acetate content of 28% is requiredto provide acceptable moistureproofing of coated paper samples. This same level of E/VA content also provides acceptable moistureproofing with E/VA copolyv mers having higher melt indices up to 500, or preferably Interpolation of vestablishes that acceptable moistureproofing is obtained with an E/VA having a melt index of 3 at a 21% level in theE/VA-wax blend.

the data from'coating runs -17 The relationship between the'melt index and the mini- 1 mum amount of B/VA required in thewax blend to' obtainf flexible coatings, as measured by the attainment of I acceptable moistureproofing of creased paper samples, is

f-summanze' d as follows v t z hgjllifl E/VA meltindex Minimum percent E/V A in wax blend The relationship between the melt index and minimum E/VA' copolymer content in the 0.1 to 500 melt index range may be expressed by the following equation:

Percent copolymer=35-15(0.9715) where MI is the melt index of the copolymer. A graph j of this equation and the four data points indicated above are shown in FIGURE 6. A comparison of the mini- I mum-percent copolymer calculated with the above equation and the experimentally determined values is indicated below;

Minimum percent copolymcr The equation thus gives calculated values within 0.3 per- Example 5 7 "An E/VA copolymer was prepared having a mole ratio of 6.4/1 (32.4% vinyl acetate) and inherent viscosity of r Polyethylene (low molecular weight) 1.17. Forty grams of this copolymer washeated'with; 60 grams of pale yellow microcrystalline wax having a' melting point of 165 F. (Multiwax ML 445, Petroleum Specialties C0,.) until a homogeneous melt wasobtained.

This melt had a viscosity of 5000 centipoises at;150 C.

and was easily coated on paper with conventional hot-melt equipment.

' Example 6 A mixture of 40 g. of 5/1 E/VA copolymer (38% 1 vinyl acetate) having an inherent viscosity of 0.96 was melted with 60 g. of paraflin wax. The resultant composition when applied to cardboard is heat-scalable and highly adherent.

The compositions of the present invention havede'monstrated marked superiority over conventional coatings.

at a weight of 84 lb./ream and the composition of Ex ample 5 was applied at 69 lb./ream. Both coated papers were repeatedly creased and tested for water vapor transmission .by standard techniques. The transmission of vapor through the papers was as follows:

Water vs transmision $7 43 hours hours IVA-wax Example 7 Conditioning of E/VA-w-ax coated paper at F. for four hours lowers the water vapor transmission of both fiat and creased samples as indicatedvin Table VIII. Data which indicate the poorer moistureproofing obtained with kraft paper are also included in the table.

-All papers coated with 40% EIVA, 60% paraflin wax blend; E/VA egmtmneii1 728%, vinyl acetate and had inherent viscosity of om; 11.1. o wax,

Example 8 Paper samples coated in Example 2 and listed in Table II were heat-sealed with a Sentinel Sealer at 250 F., 30 lb./in. for 2 seconds or with a Palo Myer Sealer according to TAPPI Standard T642 sm-S4. The seal strengths in g./in. were then determined on 1 inch wide samples at 73' F. with an Instron Tensile Tester using a crosshead speed of 5 in./min. The numerical values in parentheses reported in Table IX were the peak values obtained'initially before the paper itself fails and fiber tear is obtained. With pigment (TiO )-coated sulfite paper (25 lb./ream), fiber tear is always obtained when the seal strength value exceeds about 200 g./in.

13 14 TABLE IX The five variables and the ranges of the variables used in this design were as follows: E/VA concentration; E/vA 5-45%; coating weight, 3-27.5. lb./3000 it heat-seal Simple No b 3533 7 time, 0.5-2.5 seconds; heat-seal temperature, 180-280 F.; Percent Percent in (g./in.) 5 and heat-seal pressure, 20-40 p.s.l.g. Vinyl acetate wax blend The coated paper samples were heat-sealed to the wire- 1 side of uncoated paper using a Sentinel Heat Sealer. 'The 6 47 heat-seal conditions were varied within the ranges indiaas e 11 34.2 9 29 cated above. The sealed specimens were condltloned for g g3 2 1 24 hours at 73 F. and 50% relative humidity prior to 34.2 so 350 (420; delamination with an Instron Tensile Tester. 3 :3 353 The heat-seal data so obtained were then used to calcu- 27.7 40 260 360) late the 21 coeflicients of an equation having terms for gig 3 g (360 percent E/VA in the wax blend, coating weighnand heat- 34.2 40 440 (490; seal conditions of time, temperature and pressure for each 13 3 2g (500) of the five petroleum waxes. The equations were used to chart the effect of the E/VA concentration and coating Ref t ed ed E 1 2' T m IL weight on the quality of the heat-seal bonds for the differb seniir rel 318. .i'e%,?'$p1ee4,1fif1,n. itaio Myer Sealer ent petroleum waxes. These char-ts showed that the bond strength was dependent on the wax used at E/VA concen- {Fiber tear obtained with samples having beat-seal strength greater trations below Each wax required a different minithan 200. mum concentration of E/VA to attain a fiber-tearing The data in Table IXindicate that the amount of E/VA nd. T choice p wax a significant effect in the wax blend has a pronounced effect on the heat-seal heat-seal bond quality of coatings 1n the flexible region strengthof coated papers. Fiber tear was obtained con- 25 VA concentrations above 25%, coating weight 12-15 sistently with E/VA-wax compositions containing or 3 A b s in h region were mor EIVA; i In addition to the excellent heat-seal bonds obtained Example 9 when sealing to uncoated paper, these E/VA-wax coatings give fiber tearing bonds to polyethylene, Mylar Seal strengths were determined as in Example 8 with a 30 polyester film, cellophane and aluminum foil. series of paper samples coated with 40% E/VA-60% Small amounts of pigments, dyes and the like may be paraflin wax blends in which the percentage of vinyl ace- V added to the E/VA-wax coating compositions with retentate 1n the E/VA varied from 20 to 31.5% by weight and ion of their des1rable mo1stureproofing and heat-sealmg the inherent vlscositles of the E/VA copolymers varied to "ties Thisis Shown mum next exam 7 r from 0.9 to 1.2. The results are summarized in Table X. p p p All the samples were prepared by coating 25 lb./ream sul- Example 11 fite paper with toluene solutions of E/VA-wax containing 60% solids and heat-sealing the coated paper with a EAha-60% paraffin Wax pvmposgtwn was sentim] mas described ,i Example 3 dissolved 1n toluene to yleld a.60% solids solution. The

0 E/VA contained 28% vinyl acetate and had an inherent -X 4 viscosity of 0.97. One portion of the solution was pigmented with 10% by weight of ASP-600 clay, based on EvA'Pemnt Loading, Emmi the combined E/VA and wax. Another portion was vinyl ace -l strength pigmented with 10% by weight of a pigment-grade TiO,.

The pigmented solutions were applied to 25 lb./ream sulm 0 n 75 fite paper. The coated papers were heat-sealed using a 12 m0 Sentinel Sealer as described in Example 8. The heat-seal 13 strengths were determined as before. The results are 27.8 10 b 257 29.1 10 b 249 shown in Table XII. 31.5 16 b 225 v V TABLE XII Sealed to itself. b Fiber tear.

The data in Table x indicate that below 25% vinyl WVT 1 acetate in the E/VA cop lymer the seal trength 1s lower Pigment iiiireiii (g Ibo/109m 2,24 hm) r eil gil and fiber tear is not obtained. FM CM (14 Example 10 A SP600clny 20 1.2 1.4 5280 A statistically des1gned experiment s1m1lar to that uti- T10! 21 L5 lized inExample 3 was used to investigate further the heat-sealing properties of E/VA-wax blends. The same 'sealedmll'self- E/VA and five petroleum waxes of Example 3 were used. Example 12 v The coated paper samples described in Table IV and four vadditional coating runs summarized in Table XI Paper samples coated with E/VA- wax (Numbers 5, 6, were used in a five-variable heat-seal design. 17, and 18 from Example 2) were creased to a TABLE XI Coded Actual coating weight obtained Coating Bun values Actual No. percent EIVA X1 X1 WaxA Wax B 'Wax C Wax D Wax E 25 2.9 3.5 4.1 4.4 2.6 25 27. 9 2s. 0 27. 0 31. s 29. o 5 12.5 14.5 10.0 13.1 16.1 45 17. 1 16. 1 15. 4 13. a 14. s

I cated in Example 13.

"angle at -20 F. and cracks were detected by noting the penetration of an organic dye solution. The lowtemperature flexibility of the E/VA-wax coated papers was found to be directly dependent on the E/VA content of "the coating. At 40% or greater'E/VA, no cracks developed. Slight failure occurred at 30% E/VA and severe failure at the 20% E/VA level. v

The importance of compatibility in the ,E/VA-wax blends has already been mentioned. In addition to the reasons previously given, compatibility is important to the satisfactory extrusion coating of E/VA-wax compo! sitions. Extrusion coating requires that the strength of E/ VA copolymer which gives a homogeneous melt, that is, one whose haze point is within a few degrees of the V melting point of the wax so that a homogeneous coating is applied. a

The compatibility of the E/VA and wax also has an efiect on the grease resistance of coated papers as indiam le 13 Pigment (Tio ycoated sulfite paper was. coated with several blends of E/VA and paraflin wax (M.P. 147 -F.) with varying vinyl acetate content in the 13/ VA and varying amounts of-E/VA in the wax blend. The grease resistance of the paper was measured in a standard TAPRI test in which the time required for turpentine to I "break through the coating was determined. The results are summarized in Table XIII.

TABLE XIII Wax blend EIVA, Time (min) percent Loading, to b ATh value vinyl lb./ream through from fig- Perecnt Percent acetate coating ure 1 E/VA wax The incompatible blends, that is, the ones which have a AT greater than 5, gave coatings which were no better than the straight waxed paper control. It is noted that improved grease resistance was obtained with all of the A compatible E/VA-wax compositions including those with relativelysmall amounts (3-9% of E/VA. These latter compositions are outside the scope of my compositions which are both flexible and compatible.

Example Strips of Mylar polyester film were hot-melt coated with a compatible 40% E/VA-60% paraflin wax composition (27.6% vinyl acetate in E/VA) and an incompatible':40% E/VA60% parafiin wax composition 19.7% vinyl acetate in E/VA). After conditioning the samples at 70 C. for 80 minutes, the optical densities of the films were measured at 7000 A. wave length using a Model 10, Cary Spectrophotometer. The extinction 'coeflicients for the coatedffllms, normalized to a 1 mil coating thickness, were 0.34 and 0.61, respectively. Since clarity of the films is inversely proportional Ito the extinction coeflicient, these results indicate that the cornpatible blend gives a much clearer coating than the ineompatible blend.

If desired, a wax antioxidant, for example tert-butylhydroxyanisole, may be added to my compositions at a concentration of about 25 p.p.m. to provide stability against oxidative degradation, particularly at elevated temperatures up to about 200 C.

The properties shown by my mixture of E/VA and wax are unique and unexpected. The compositions, when blended in the proportions within the closed area ABCD of FIGURE 1 and with E/ VA copolymers having the required melt index range, are tough, flexible materials which,when coated on paper or paperboard, havemany applications in the packaging industry. The coatings retain their moistureproofing properties even after flexing and can be heat-sealed to give strong bonds. The coatings can be pigmented and they provide improvedgrease resistance over unmodified wax coatings. Paper, paperboard, and other flexible substrates coated with the compositions of this invention can be used in milk cartons,

ages for dry foods, heat-scalable aluminum .overwraps and heat-scalable labels.

In addition to the flexible and heat-scalable assemblies obtainable by coating the E/VA-wax compositions ofthis invention on paper or other flexible substrates, the compositions of the invention can also be used to make molded and shaped articles. In this application, use is made of the surprising tensile strength and elongation exhibited by the compositions, even though they may consist of more than 50% of an economical petroleum wax. For example, the tensile strength and percent elongation at break of a homogeneous blend of 40% of an:

E/VA' having a vinyl acetate content of 28% and melt index-of 15 and 60% of paraflin'wax areabout 750 lb./in. and respectively. I

Shaped 'or molded articles may be preparedtrom E/VA-wax compositions by standard manufacturing techniques, for example, by conventional injection molding.

Another method, known as flush molding, can also be used. In this method, a molten E/VA-wax blend at about C. is poured into a split mold which is cooled either by ambient conditions or by immersion of the outer jacket in water. The E/VA-wax melt, solidifies from the walls of the split mold inward. The length of time the melt is left in the mold determinesthe wall thickness of the object formed. After a pre-determined.time, the split mold is inverted and the melt which'has not solidified is poured out. .The formed object is allowed to solidify completely and is then removed from the mold.

The E/VA-wax compositions of this invention are also of value as hot-melt adhesives.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A flexible and compatible composition consisting essentially of petroleum wax and a copolymer; of ethylene and vinyl acetate, said copolymer having a melt index of 0.1 to 500, the weight percentages of said waxand said copolymer in said composition and the weight-percentage .of vinyl acetate in said copolymer being representedby a point within the closed area ABCD oi FIGURE 1, which composition has a minimum copolymer content defined by the equation:

Percent copolymer=35-15 (0.97 15 5., A homogeneous melt consisting essentiallyof pe troleum wax and a copolymer of ethylene and vinyl acetate, the haze point of said melt being within 5 C. of the melting point of said wax, the weight, percentages of said wax and said copolymer in said melt and the weight percentage of vinyl acetate in said copolymer being represented by a point within the closed area ABCD of FIGURE 1, which melt has a minimum copolymer content defined by the equation:

Percent copolymer: 35-15((19715) where MIrepresents the melt index of the copolymer, said copolymer having amelt index of 0.1 to 500.

6. The melt of claim in which the petroleum wax is paraflin wax.

7. The melt of claim 5 in which the petroleum wax is microcrystalline wax.

8. A flexible and compatible composition consisting essentially of petroleum wax and a copolymer of ethylene and vinyl acetate, said copolymer having a melt index of 0.1 to 500, the weight percentages of said wax and said copolymer in said composition and the weight percentage of vinyl acetate in said copolymer being represented by a point within the closed area BCEF of FIGURE 1.

9. The composition of claim 8 in which the copolymer of ethylene and vinyl acetate has a melt index of 0.1 to 200.

10. The composition of claim 9 in which the petroleum wax is paraflln wax.

' 11; The composition of claim 9 in which the petroleum wax is microcrystalline wax.

- 12.'A flexible and compatible composition consisting essentially of 60 weight percent of petroleum wax and 40 weight percent of a copolymer of ethylene and vinyl acetate, said copolymer containing 28 to 35 weight percent of'copolymerized vinyl acetate and having a melt index of 0.1 to 200.

13. A flexible and heat-scalable assembly comprising .a flexible substrate and a coating composition thereon,

Percent copolymer 35-15(0.9715) where MI represents the melt index of the copolymer. 14. A flexible and heat-scalable assembly according to claim 13 in which the flexible substrate is paper.

15. A flexible and heat-sealable substrate according to claim 14 in which the petroleum wax is paraflin wax.

16. A flexible and heat-sealable assembly comprising a paper substrate and a coating composition thereon, said coating composition consisting essentially of petroleum wax and a copolymer of ethylene and vinyl acetate, said copolymer having a melt index of 0.1 to 500, the weight percentages of said wax and said copolymer in said composition and the weight percentage of vinyl acetate in said copolymer being represented by a point within the closed are a ABCD of FIGURE 1, which coating composition has a minimum copolymer content defined by the equation:

Percent copolymer=35-l5 (0.9715

where MI represents the melt index of the copolymer, the assembly having a diiferential of not more than 0.75 g./ 100 in. /24 hrs. between the fiat and creased water vapor transmission rates.

17. A shaped article comprising a flexible and compatible composition consisting essentially of petroleum wax and a copolymer of ethylene and vinyl acetate, said copolymer having a melt index of 0.1 to 500, the weight percentages of said wax and said copolymer in said composition and the weight percentage of vinyl acetate in said copolymer being represented by a point within the closed area ABCD of FIGURE 1, which composition has a minimum copolymer content defined by the equation:

Percent copolymer=' 35-15(0.9715

where MI represents the melt index of the copolymer.

18. A shaped article according to claim 17 in which thepetroleum wax is paraflin wax.

19. A shaped article comprising a flexible and compatible composition consisting essentially of petroleum wax and a copolymer of ethylene and vinyl acetate, said co polymer having a melt index of 0.1 to 500, the weight percentage of said wax and said copolymer in said composition and the weight percentage of vinyl acetate in said copolymer being represented by a point within the closed area BCEF of FIGURE 1.

20. A shaped article according to claim 19 in which the petroleum wax is paraffin wax.

21. A heat-scalable flexible sheet material having on one surface thereof a thermoplastic wax composition coating having a melt viscosity of between 2000 and 15,000 centipoises measured at 290 F., said wax composition comprising between about and of a petroleum wax having a melting point between about F. and F., and between about 50% and 30% of a copolymer of ethylene and vinyl acetate, said copolymer being the copolyrnerization product of ethylene and vinyl acetate in ratio between about 2 to 1 and 4 to 1.

References Cited by the Examiner UNITED STATES PATENTS 2,877,196 3/59 Reding 26028.5 3,048,553 8/62 Moss 26028.5

MORRIS LIEBMAN, Primary Examiner. 

21. A HEAT-SEALABLE FLEXIBLE SHEET MATERIAL HAVING ON ONE SURFACE THEREOF A THERMOPLASTIC WAX COMPOSITION COATING HAVING A MELT VISCOSITY OF BETWEEN 2000 AND 15,000 CENTIPOISES MEASURED AT 290*F., SAID WAX COMPOSITION COMPRISING BETWEEN ABOUT 50% AND 70% OF A PETROLEUM WAX HAVING A MELTING POINT BETWEEN ABOUT 130*F. AND 170*F., AND BETWEEN ABOUT 50% AND 30% OF A COPOLYMER OF ETHYLENE AND VINYL ACETATE, SAID COPOLYMER BEING THE COPOLYMERIZATION PRODUCT OF ETHYLENE AND VINYL ACETATE IN RATIO BETWEEN ABOUT 2 TO 1 AND 4 TO
 1. 